EP2091886A1 - Procede de fabrication de clinker a emission de co2 controlee - Google Patents
Procede de fabrication de clinker a emission de co2 controleeInfo
- Publication number
- EP2091886A1 EP2091886A1 EP07858641A EP07858641A EP2091886A1 EP 2091886 A1 EP2091886 A1 EP 2091886A1 EP 07858641 A EP07858641 A EP 07858641A EP 07858641 A EP07858641 A EP 07858641A EP 2091886 A1 EP2091886 A1 EP 2091886A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- rotary kiln
- calcination
- fumes
- combustion
- precalcination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000008569 process Effects 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 238000002485 combustion reaction Methods 0.000 claims abstract description 48
- 238000001354 calcination Methods 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000003517 fume Substances 0.000 claims description 47
- 239000002994 raw material Substances 0.000 claims description 20
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 2
- 239000000779 smoke Substances 0.000 claims 1
- 239000003546 flue gas Substances 0.000 abstract 5
- 239000004568 cement Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000792859 Enema Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007920 enema Substances 0.000 description 1
- 229940095399 enema Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/364—Avoiding environmental pollution during cement-manufacturing
- C04B7/367—Avoiding or minimising carbon dioxide emissions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0233—Other waste gases from cement factories
Definitions
- the present invention relates to a clinker manufacturing method for controlling CO 2 emissions into the atmosphere.
- Clinker manufacturing processes are among the most emitting industrial processes of CO 2 , in the same proportions as the steel industry. They each account for about 5% of anthropogenic CO 2 emissions. This large quantity of CO 2 waste for the cement plant comes not only from the intensive energy consumption in the clinker making process, but especially from the limestone calcination reaction, which releases a very large amount of CO 2 (0 , 5 tons of CO 2 produced by this mechanism for each ton of clinker produced). The introduction of new regulations under the Kyoto Protocol requires the various countries that have ratified this protocol to reduce these CO 2 emissions, according to set objectives per period.
- the object of the present invention is to provide a clinker manufacturing process for recovering combustion fumes produced by this method so as to eliminate CO 2 at a cost effective.
- the invention relates to a method of manufacturing clinker from a raw material using:
- Raw or raw material consists mainly of limestone and silica.
- this raw material is preheated by combustion fumes, for example by introducing the raw material at the top of cyclones in which the raw material is brought into contact with hot combustion fumes.
- the raw material is precalcined: by the formation of heat by combustion, the partial calcination of the preheated raw material is obtained according to the following reaction: CaCO ⁇ - »CaO + O
- the fumes generated during precalcination generally serve to preheat the raw material during the first preheating stage. These combustion fumes generally have a CO 2 concentration of at least 30% by volume.
- these precalcined materials then continue their way through the rotary kiln, in which they are transformed into clinker through a reaction between lime and silica at a very high temperature (> 1450 ° C). The heat required for this third step is provided by combustion at the bottom end of the rotary kiln.
- This third step also creates combustion fumes comprising CO 2 in a concentration generally of at most 15%.
- a CO 2 removal treatment is carried out on the combustion fumes created by the second precalcination stage without mixing the said fumes with the combustion fumes created by the calcination in the rotary kiln.
- This characteristic is different from the implementation of the prior art, where the fumes generated by the calcination in the rotary kiln then circulate upstream through the precalcination device and the preheating space of the raw materials, mixing with combustion fumes from precalcination.
- the fumes from the calcination in the rotary kiln are not transmitted to the precalciner. On the other hand, they are subject to energy recovery. The first two stages are thus totally separated from the third stage.
- the combustion fumes created by the calcination in the rotary kiln are directly removed from the process without coming into contact with the products of the first and second stages.
- the heat present in the combustion fumes of calcination implemented in the rotary kiln can be upgraded according to different options.
- a first option at least a portion of the combustion fumes created by the calcination in the rotary kiln can preheat the crop indirectly.
- at least a portion of the combustion fumes created by the calcination in the rotary kiln can preheat the reactants introduced into the rotary kiln indirectly.
- "indirectly" means that the combustion fumes created by the calcination in the rotary kiln are not mixed with the material to be heated: the preheating is done through a wall separating the fumes of the material to be heated.
- Indirect preheating makes it possible to avoid mixing the combustion fumes of the precalcination and the rotary kiln according to the invention.
- the indirect exchange can be done by any type of heat exchanger known between the raw or precalcined cru with the combustion fumes from the rotary kiln.
- at least one Part of the combustion fumes created by calcination in the rotary kiln can be used in a boiler or heat recovery unit.
- precalcination of the raw material implements oxycombustion.
- oxycombustion is meant a combustion carried out using a fuel and an oxidant having an oxygen concentration of greater than 21%, preferably greater than 25%.
- Such an oxidant may be a mixture of air and oxygen in suitable proportions.
- Oxyfuel combustion enriches combustion fumes with CO 2 in the first and second stages.
- the concentration of CO 2 in the fumes resulting from this oxycombustion is generally greater than 50% by volume.
- the oxidant used during the oxyfuel combustion is pure oxygen.
- Pure oxygen is understood to mean an oxygenated gas comprising at least 90% oxygen.
- This preferred implementation makes it possible to obtain combustion fumes having a CO 2 concentration of greater than 90% after condensation. Such condensed fumes then require no treatment by a more advanced CO 2 removal process. They can then be partially recycled in the precalcination stage in order to increase the gas flow within the first two stages and maintain good convective heat exchange conditions.
- the invention therefore also covers the case where the fumes resulting from the oxycombustion are condensed and the condensed fumes are at least partially recycled in the precalcination of the raw material.
- the implementation of the invention makes it possible to concentrate in CO 2 the combustion fumes originating from the preheating and precalcination zones.
- 50 to 90% of the global volume of CO 2 generated by the cement plant can be grouped together at the level of the entire precalcination device and the preheater, within a flow of combustion fumes whose flow rate is less than half to that of a cement plant according to the prior art; this difference makes the use of CO 2 removal processes much more cost-effective, even in the current state of technology, since disposal processes thus treat lower flow rates at higher CO 2 concentrations, which are generally at least greater than 40% by volume.
- the costs of the processes for removing CO 2 from the combustion fumes are even lower because of the reduced flow rate of fumes and their even higher concentration of CO 2 , which is generally at least greater than 50% by volume.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Biodiversity & Conservation Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental Sciences (AREA)
- Public Health (AREA)
- Ecology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Treating Waste Gases (AREA)
- Furnace Details (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Muffle Furnaces And Rotary Kilns (AREA)
- Carbon And Carbon Compounds (AREA)
- Treatment Of Sludge (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL07858641T PL2091886T3 (pl) | 2006-11-09 | 2007-10-22 | Sposób wytwarzania klinkieru z kontrolowaną emisją co2 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0654794A FR2908327B1 (fr) | 2006-11-09 | 2006-11-09 | Procede de fabrication de clinker a emission de co2 controlee |
PCT/FR2007/052219 WO2008056068A1 (fr) | 2006-11-09 | 2007-10-22 | Procede de fabrication de clinker a emission de co2 controlee |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2091886A1 true EP2091886A1 (fr) | 2009-08-26 |
EP2091886B1 EP2091886B1 (fr) | 2017-05-10 |
Family
ID=37814632
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07858641.9A Active EP2091886B1 (fr) | 2006-11-09 | 2007-10-22 | Procede de fabrication de clinker a emission de co2 controlee |
Country Status (17)
Country | Link |
---|---|
US (1) | US8187374B2 (fr) |
EP (1) | EP2091886B1 (fr) |
JP (1) | JP2010509166A (fr) |
KR (1) | KR20090097852A (fr) |
CN (1) | CN101541702B (fr) |
AU (1) | AU2007316519B2 (fr) |
BR (1) | BRPI0718854A2 (fr) |
CA (1) | CA2668937C (fr) |
EG (1) | EG26139A (fr) |
ES (1) | ES2634264T3 (fr) |
FR (1) | FR2908327B1 (fr) |
MA (1) | MA31281B1 (fr) |
MX (1) | MX2009004873A (fr) |
PL (1) | PL2091886T3 (fr) |
RU (1) | RU2469969C2 (fr) |
WO (1) | WO2008056068A1 (fr) |
ZA (1) | ZA200902776B (fr) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2934589B1 (fr) | 2008-08-01 | 2010-08-27 | Fives Fcb | Procede de fabrication de clinker de ciment dans une installation, et installation de fabrication de clinker de ciment en tant que telle |
FR2934590B1 (fr) * | 2008-08-01 | 2010-08-13 | Fives Fcb | Procede de fabrication de clinker de ciment dans une installation, et installation de fabrication de clinker de ciment en tant que telle. |
DE102008053135B3 (de) | 2008-10-24 | 2010-07-01 | Polysius Ag | Verfahren und Anlage zur Herstellung von Zementklinker |
FR2947542B1 (fr) * | 2009-07-02 | 2011-07-29 | Fives Fcb | Procede de fabrication de clinker de ciment dans une installation et installation de fabrication de clinker de ciment en tant que telle |
JP4678449B1 (ja) * | 2009-10-20 | 2011-04-27 | 三菱マテリアル株式会社 | セメント製造設備におけるco2ガスの回収方法および回収設備並びにセメントの製造方法 |
WO2011048770A1 (fr) * | 2009-10-20 | 2011-04-28 | 三菱マテリアル株式会社 | Procédés et systèmes pour la récupération de co2 gazeux dans des installations de fabrication de ciment et procédés de fabrication de ciment |
JP5348790B2 (ja) * | 2010-02-22 | 2013-11-20 | 太平洋セメント株式会社 | セメント焼成方法及び焼成装置 |
CN101792276B (zh) * | 2010-02-25 | 2011-12-21 | 东南大学 | 适合分离捕集co2的部分全氧型水泥生产方法 |
DE102012105977B4 (de) * | 2012-07-04 | 2015-11-05 | Thyssenkrupp Industrial Solutions Ag | Verfahren und Anlage zur Herstellung von Zementklinker aus Zementrohmehl |
RU2555980C2 (ru) * | 2012-08-10 | 2015-07-10 | Федеральное государственное бюджетное учреждение науки Объединенный институт высоких температур Российской академии наук (ОИВТ РАН) | Способ производства цементного клинкера |
CN103253879B (zh) * | 2013-05-07 | 2015-04-22 | 华南理工大学 | 一种采用o2/co2燃烧技术富集co2的水泥熟料生产工艺 |
WO2015077818A1 (fr) * | 2013-11-29 | 2015-06-04 | Calix Ltd | Procédé et appareil pour la fabrication de ciment portland |
CN104091223A (zh) * | 2014-06-11 | 2014-10-08 | 北京可视化节能科技有限公司 | 水泥企业碳排放管理系统 |
GB201904480D0 (en) * | 2019-03-29 | 2019-05-15 | Origen Power Ltd | Calcination process |
RU2740349C1 (ru) * | 2020-04-24 | 2021-01-13 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела и механохимии Сибирского отделения Российской академии наук | Способ безотходного сжигания углеродного топлива |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3498594A (en) * | 1966-10-17 | 1970-03-03 | Sophus Rikhof | Cement burning process and apparatus |
JPS49117517A (fr) * | 1973-03-14 | 1974-11-09 | ||
CS166580B1 (fr) * | 1973-10-29 | 1976-03-29 | ||
DE2712238C2 (de) * | 1977-03-21 | 1988-05-05 | Klöckner-Humboldt-Deutz AG, 5000 Köln | Verfahren und Vorrichtung zum mehrstufigen Erbrennen von Zementklinker |
US4548580A (en) * | 1981-12-04 | 1985-10-22 | Mitsubishi Jukogyo K.K. | Calcining apparatus for powdery materials |
JPS5899148A (ja) * | 1981-12-04 | 1983-06-13 | 三菱鉱業セメント株式会社 | 粉状物質の仮焼装置 |
JPS5899151A (ja) * | 1981-12-04 | 1983-06-13 | 三菱鉱業セメント株式会社 | 粉状物質の化焼装置 |
JPS5899149A (ja) * | 1981-12-04 | 1983-06-13 | 三菱鉱業セメント株式会社 | 粉状物質の仮焼装置 |
JPS5899150A (ja) * | 1981-12-04 | 1983-06-13 | 三菱鉱業セメント株式会社 | 粉状物質の仮焼装置 |
DE3341695A1 (de) * | 1983-11-18 | 1985-05-30 | Klöckner-Humboldt-Deutz AG, 5000 Köln | Verfahren und anlage zum brennen von feinkoernigem gut, insbesondere zur herstellung von zementklinker aus zementrohmehl |
JPS6256340A (ja) * | 1985-08-29 | 1987-03-12 | 株式会社神戸製鋼所 | セメント原料粉末の焼成装置 |
JPS6259389A (ja) * | 1985-09-09 | 1987-03-16 | 株式会社神戸製鋼所 | 複数系統型粉末原料予熱装置 |
JPS6259390A (ja) * | 1985-09-09 | 1987-03-16 | 株式会社神戸製鋼所 | 複数系統型粉末原料予熱装置 |
US5662050A (en) * | 1995-05-05 | 1997-09-02 | Angelo, Ii; James F. | Process for chemical/thermal treatment without toxic emissions |
JPH09110485A (ja) * | 1995-10-09 | 1997-04-28 | Ishikawajima Harima Heavy Ind Co Ltd | セメント製造設備 |
EP1092691A1 (fr) * | 1999-09-16 | 2001-04-18 | "Patelhold" Patentverwertungs-& Elektro-Holding AG | Procédé de fabrication de clinker à partir de farine crue et de gaz provenant d'une gazéfication de charbon |
JP2002173349A (ja) * | 2000-12-06 | 2002-06-21 | Hitachi Cement Kk | セメント原料の焼成方法および焼成装置 |
WO2002083591A1 (fr) * | 2001-04-13 | 2002-10-24 | Co2 Solution Inc. | Procede et usine de production de clinker de ciment portland |
US6935251B2 (en) * | 2002-02-15 | 2005-08-30 | American Air Liquide, Inc. | Steam-generating combustion system and method for emission control using oxygen enhancement |
ES2192994B1 (es) * | 2002-03-22 | 2005-02-16 | Consejo Superior Investig. Cientificas | Procedimiento de combustion con separacion integrada de co2 mediante carbonatacion. |
US7066728B2 (en) * | 2003-01-21 | 2006-06-27 | American Air Liquide, Inc. | Process and apparatus for oxygen enrichment in fuel conveying gases |
DE10358317A1 (de) * | 2003-12-12 | 2005-07-14 | Polysius Ag | Anlage und Verfahren zur thermischen Behandlung von Rohmaterial |
US7279039B2 (en) * | 2004-12-30 | 2007-10-09 | Envirocare International, Inc. | Method and apparatus for controlling pollution from a cement plant |
-
2006
- 2006-11-09 FR FR0654794A patent/FR2908327B1/fr not_active Expired - Fee Related
-
2007
- 2007-10-22 CN CN2007800415563A patent/CN101541702B/zh active Active
- 2007-10-22 AU AU2007316519A patent/AU2007316519B2/en not_active Ceased
- 2007-10-22 KR KR1020097009482A patent/KR20090097852A/ko not_active Application Discontinuation
- 2007-10-22 CA CA2668937A patent/CA2668937C/fr active Active
- 2007-10-22 BR BRPI0718854-4A2A patent/BRPI0718854A2/pt not_active IP Right Cessation
- 2007-10-22 RU RU2009121811/03A patent/RU2469969C2/ru not_active IP Right Cessation
- 2007-10-22 MX MX2009004873A patent/MX2009004873A/es active IP Right Grant
- 2007-10-22 JP JP2009535774A patent/JP2010509166A/ja active Pending
- 2007-10-22 US US12/513,997 patent/US8187374B2/en active Active
- 2007-10-22 ES ES07858641.9T patent/ES2634264T3/es active Active
- 2007-10-22 PL PL07858641T patent/PL2091886T3/pl unknown
- 2007-10-22 WO PCT/FR2007/052219 patent/WO2008056068A1/fr active Application Filing
- 2007-10-22 EP EP07858641.9A patent/EP2091886B1/fr active Active
-
2009
- 2009-04-21 ZA ZA2009/02776A patent/ZA200902776B/en unknown
- 2009-05-06 EG EG2009050659A patent/EG26139A/en active
- 2009-06-05 MA MA31960A patent/MA31281B1/fr unknown
Non-Patent Citations (1)
Title |
---|
See references of WO2008056068A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP2091886B1 (fr) | 2017-05-10 |
AU2007316519A1 (en) | 2008-05-15 |
RU2469969C2 (ru) | 2012-12-20 |
ZA200902776B (en) | 2010-02-24 |
MX2009004873A (es) | 2009-05-19 |
CN101541702B (zh) | 2012-11-21 |
RU2009121811A (ru) | 2010-12-20 |
FR2908327B1 (fr) | 2009-01-30 |
FR2908327A1 (fr) | 2008-05-16 |
ES2634264T3 (es) | 2017-09-27 |
CN101541702A (zh) | 2009-09-23 |
CA2668937C (fr) | 2014-12-23 |
EG26139A (en) | 2013-03-26 |
PL2091886T3 (pl) | 2017-10-31 |
JP2010509166A (ja) | 2010-03-25 |
KR20090097852A (ko) | 2009-09-16 |
US20100000446A1 (en) | 2010-01-07 |
BRPI0718854A2 (pt) | 2014-02-25 |
US8187374B2 (en) | 2012-05-29 |
WO2008056068A1 (fr) | 2008-05-15 |
MA31281B1 (fr) | 2010-04-01 |
AU2007316519B2 (en) | 2013-05-23 |
CA2668937A1 (fr) | 2008-05-15 |
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